EP3011310B1 - Système pour l'analyse de mercure - Google Patents

Système pour l'analyse de mercure Download PDF

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Publication number
EP3011310B1
EP3011310B1 EP14813771.4A EP14813771A EP3011310B1 EP 3011310 B1 EP3011310 B1 EP 3011310B1 EP 14813771 A EP14813771 A EP 14813771A EP 3011310 B1 EP3011310 B1 EP 3011310B1
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Prior art keywords
sample
measurement cell
gas
analyzer
mercury
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German (de)
English (en)
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EP3011310A4 (fr
EP3011310A1 (fr
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Philip J. DUFRESNE
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0045—Hg
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/3103—Atomic absorption analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/3103—Atomic absorption analysis
    • G01N2021/3107—Cold vapor, e.g. determination of Hg

Definitions

  • the present invention relates to a system for measuring mercury in samples of various matrices such as gaseous, aqueous, complex such as oils, and solids including sorbent traps used to measure the mercury concentration from emission sources such as coal-fired power plants, cement kilns and other emission sources.
  • various matrices such as gaseous, aqueous, complex such as oils, and solids including sorbent traps used to measure the mercury concentration from emission sources such as coal-fired power plants, cement kilns and other emission sources.
  • JP 2010096688 and DE 19506875 disclose mercury analyzer systems comprising mercury vapor analyzers for detecting the mercury concentration in mercury effluent gas vaporized using a furnace and sample boat. JP 2010096688 further discloses a pump for drawing the effluent gas into a measurement cell and an optical bench for directing an analytical beam generated by the mercury vapor.
  • Mercury Instruments USA: "Mercury Laboratory Analyzer LA 254 " discloses similar mercury analyzer systems, however it discloses the use of an impinger, rather than a furnace and sample boat, to produce the mercury sample effluent from an aqueous mercury sample.
  • EP 2369335 discloses the use of an atomic absorption spectrometer for analyzing mercury effluent gas drawn into a measurement cell using a vacuum pump.
  • a further mercury analyzer is disclosed in JP S58 1149 U .
  • an analyzer system for measuring mercury including a mercury vapor analyzer for generating and detecting analytical beams; an optical bench mounted to a mercury vapor analyzer into which a measurement cell can be positioned so that the analytical beams can traverse the measurement cell, interact with a sample effluent gas and return to the vapor analyzer where the amount of mercury in the sample effluent gas can be determined; a pump station to draw the sample effluent gas from the measurement cell; a furnace mounted to the measurement cell; a sample boat to contain a sample adapted to be disposed within the furnace to release the sample effluent gas from the samples into the measurement cell; and an exhaust gas conditioner to receive the sample effluent gas from the measurement cell and to cool the sample gas so as to condense any excess moisture carried in the sample gas, wherein the exhaust gas conditioner includes: a heat exchanger which receives and cools a heated exhaust gas from the measurement cell; and a thermoelectric cooler to cool fluid within the exhaust gas conditioner such that cooling the sample gas drawn
  • an analyzer system for measuring mercury within aqueous samples, including: a mercury vapor analyzer for generating and detecting analytical beams; an impinger for mixing aqueous samples containing mercury with a stannous chloride solution, the impinger including a vessel closed with a cap having an air inlet and an outlet; a measurement cell connected at a first end to the outlet of the impinger and at a second end to a vacuum pumping system; and an optical bench mounted to the mercury vapor analyzer into which a measurement cell is placed in a path traveled by the analytical beams projected out of the vapor analyzer whereby the analytical beams traverse the measurement cell, interact with the sample effluent of the impinger directed into the cell from the outlet of the impinger and out of the cell through the outlet of the cell.
  • a method for measuring mercury vapor comprising: generating analytical beams with a mercury vapor analyzer; releasing sample effluent gas from a sample into the measurement cell; projecting the analytical beams from the vapor analyzer through the measurement cell to interact with the sample effluent gas and returning the analytical beams back to the vapor analyzer where the amount of mercury in the sample effluent gas can be determined; and drawing the sample effluent gas from the measurement cell; wherein the sample effluent gas is generated by heating the sample in a sample boat disposed within a furnace; and receiving and cooling the sample effluent gas from the measurement cell in an exhaust gas conditioner so as to condense any excess moisture carried in the sample gas, wherein a heat exchanger of the exhaust gas conditioner receives and cools a heated exhaust gas from the measurement cell; and a thermoelectric cooler of the exhaust gas conditioner cools fluid within the exhaust gas conditioner such that cooling the sample gas drawn from the measurement cell to near ambient improves regulation of the gas drawn from the
  • exemplary dimensions may be presented for an illustrative embodiment of the invention.
  • the dimensions should not be interpreted as limiting. They are included to provide a sense of proportion. Generally speaking, it is the relationship between various elements, where they are located, their contrasting compositions, and sometimes their relative sizes that is of significance.
  • the present invention relates to an analyzer system 10 and 180 for measuring mercury in samples of various matrices such as solids including sorbent traps that have been used to collect the mercury from emission sources such as coal-fired power plants and cement kilns, and aqueous samples.
  • various matrices such as solids including sorbent traps that have been used to collect the mercury from emission sources such as coal-fired power plants and cement kilns, and aqueous samples.
  • a schematic of analyzer system 10 for measuring mercury includes a commercial or custom mercury vapor analyzer 12 connected to a computer 14.
  • An optical bench 16 (either single pass or multi-path) is securely mounted to the commercial or custom mercury vapor analyzer 12.
  • the analyzer system 10 allows the mercury released from the samples with either thermal or aqueous apparatus (depending on the matrix of the sample) to be measured with the mercury vapor analyzer 12 and analyzed with the computer 14.
  • An optical bench 16 is securely fastened to the mercury vapor analyzer 12 so that the analytical beam(s) projected out of the analyzer can reliably travel from their source 18 and then back to the optical detector 20 in the mercury vapor analyzer 12.
  • the optical bench 16 is disposed so that a measurement cell 22 can be placed in the path of the analytical beam(s) projected out from the mercury vapor analyzer 12.
  • the analytical beams from source 18 can traverse the inside of the measurement cell 22 to interact with the sample effluent released in a furnace 24 and then return back to the optical detector 20 in the mercury vapor analyzer 12 to be analyzed with the computer 14.
  • the measurement cell 22 is mounted to a furnace 24 which can have two temperature sections 26 and 28 into which a sample boat 30 into which a sample such as, for example, a section of a sorbent trap can be disposed.
  • the heat from the furnace 24 causes an effluent of sample gas from the sample to be released into measurement cell 22 for analysis by the mercury vapor analyzer 12.
  • a furnace controller 32 can be connected to furnace 24 by two power cords 34 and 36, to control the low and high temperature sections 26 and 28, respectively.
  • Two thermocouples 38 and 40 are connected at one end to the low and high temperature sections 26 and 28, respectively, and at the other end to furnace controller 32 to control the temperature in each of the temperature sections.
  • a gas line 42 connects the measurement cell 22 to a thermo-electric cooled exhaust gas conditioner 44 which cools the heated sample gases generated in the furnace 24 and directed into the measurement cell 22.
  • the heated sample gases are withdrawn from the measurement cell 22 through the gas line 42 and directed to the exhaust gas conditioner 44.
  • the hot sample gases are cooled in the exhaust gas conditioner 44 so as to condense any excess moisture carried in the sample gases. This is important because the change in state from the steam in the heated sample gases to water can cause a change in the flow rate of the sample gases being withdrawn from the measurement cell 22. It is important that the water in the hot sample gases condense quickly before mercury comes out of the sample being tested.
  • the resulting exhaust gas at near ambient temperature then flows from the thermo-electric cooled, exhaust gas conditioner 44 through a gas line 46 to a filter 48 which contains soda lime, iodinated charcoal and or charcoal to scrub the sample gases of acid gases and mercury.
  • the resulting exhaust gas then flows from filter 48 through a gas line 50 and then through a mass flow controller 52, such as a Whisper series laminar flow element mass flow controller manufactured by Alicat Scientific, Inc. of Arlington, Arizona.
  • a mass flow controller 52 such as a Whisper series laminar flow element mass flow controller manufactured by Alicat Scientific, Inc. of Arlington, Arizona.
  • the laminar flow element mass flow controller 52 precisely regulates the flow of gas through the analyzer system 10 despite the low differential pressure between the flow controller inlet and outlet inherent in this design.
  • the mass flow controller 52 regulates by either mass or volume.
  • the sample gas is then drawn through a line 54 from the mass flow controller 52 into a pump station 56.
  • the resulting sample gas exits the pump (not shown) located inside the pump station 56 through a line and passes through a muffler (not shown) which suppresses the sound of the exhaust.
  • the pump station 56 includes a high powered pump which can pump >20 liters/minute (l/m) while the present embodiment may often, or at times only require a flow rate of a fraction of this flow amount. Therefore, the pump station 56 includes an air inlet 60 that can be controlled to allow more or less air through the pump station 56 into the pump to mix with the gases from line 54.
  • a base support 70 can be a rectangular shaped tube having an upstanding tube support 74 mounted to one end and a prism/lens support 76 mounted to the opposite end.
  • the upstanding tube support 74 includes a hollow tube 78 that is securely mounted into an opening formed in the side of the analyzer 12, as shown in Figure 4 .
  • the outgoing beams generated by the beam source (not shown) in the analyzer 12 project through the hollow tube 78, pass through the measurement cell 22, as discussed hereinafter, and are turned 180 degrees on a separate path by the prism 82 mounted in the prism/lens support 76 and focused by the lens 84 so that they can travel back to an optical detector (not shown) located within the analyzer 12 and aligned with the tube 78.
  • the lens 84 and prism 82 are placed adjacent to each other such that the outgoing beams from the analyzer 12 pass through the cell 22, as discussed hereinafter, are turned 180 degrees on a separate path by the prism 82 and focused by the lens 84 so that the beams can travel back to the optical detector in the analyzer.
  • the length of the optical bench 16 is about 10 cm to about 20 cm and preferably about 15 cm to about 18 cm to work with the beam dispersion properties of the analyzer 12, such as a Lumex analyzer from Lumex Ltd. of St. Russia. But it is within the terms of the preferred embodiment that the optical bench 16 could be extended to about 35 cm with additional optical elements allowing the use of a measurement cell 180, see Figure 13 , of about 30 cm in length that would be beneficial for analyzing low-level water samples which would enable measurements of mercury in water at 0.5 nanogram (ng)/liter (L) or lower.
  • a key component of the present invention is the thermal analysis device 90, as shown in Figure 5 .
  • the thermal analysis device 90 has an enclosed housing 92.
  • a measurement cell 94 (compare 22 in Figure 1 ) is mounted to a tubular fitting 96 which extends through a rear wall 92a of housing 92 and is mounted to an end of an oven component 100 (compare 24 in Figure 1 ) disposed within the enclosed housing.
  • the oven or furnace component 100 is constructed of an elongated sample desorption tube 102 connected at one end to the tubular fitting 96 which in turn is mounted to the measurement cell 94.
  • a first bendable resistance-heating coil 104 is tightly wrapped around a first heating section or heated zone 102a (compare 26 in Figure 1 ) of the sample desorption tube 102 and a second bendable resistance-heating coil 106 is tightly wrapped around a second heating section or heated zone 102b (compare 28 in Figure 1 ) of the sample desorption tube 102.
  • the first resistance-heating coil 104 is disposed closer to the open end 102c of the tube 102 and the second resistance-heating coil 106 is disposed closer to the measurement cell 94.
  • the open end 102c of the sample desorption tube 102 can be accessed through opening 95 through the wall of enclosed housing 92, as shown in Figure 7 .
  • the two heating coils 104 and 106 are connected via suitable high-temperature wires (not shown), to the receptacles 109, 110 that are in turn connected via power cords 111, 112, respectively, to wired receptacles 113, 114 which in turn are connected to relays controlled by the PID temperature controllers 115, 116 in the control device 32, as shown in Figure 7 .
  • Two thermocouples (not shown) are secured inside the sample desorption tube 102, one placed to measure the temperature at the front or first heated zone 102a under the heating coil 104, the other at the rear or second heated zone 102b under the heating coil 106.
  • thermocouples are connected via receptacles and thermocouple wires 117, 118 to their respective PID controllers 115,116 in control device 32.
  • the pair of heating coils 104, 106 allow the front zone 102a and the rear zone 102b of the sample desorption tube 102 to be at different temperatures or if needed, to ramp up the temperatures of one or the other or both of the front and/or rear heat zones, 102a,102b, respectively.
  • the measurement cell 94 (compare 22 in Figure 1 ), as shown in Figure 5 , is constructed of a tube 108 mounted to the tubular fitting 96 and sealed on both ends by windows 119, 120 made of quartz or other suitable material transparent to the wavelengths used. Screw caps 115, 117 hold the windows 119,120 in place with washers and graphite gaskets pressing the windows onto additional gaskets made of graphite or other suitable material (not shown) so that the measurement cell 94 is essentially "air-tight" aside from the open end 102c at the end of the sample desorption tube 102, (see Figure 6 ), and an exhaust outlet 122 in the back of the measurement cell 94 that is ideally offset from the tube 96 connecting the measurement cell to the sample desorption tube.
  • the exposed screw-on window holders 115,117 make window removal and cleaning easier even when hot as compared to bayonet type fittings on other prior art instruments.
  • the thermal analysis device 90 consists of a hollow "T" shaped metal (stainless steel or other material inert to mercury at operating conditions) structure integrating the oven component 100 or sample desorption tube 102 with the measurement cell 94.
  • the inner diameter of the sample desorption tube 102 is large enough so that air flowing though the tube from open end 102c at a high flow rate between about 4 L/minute and 40 L/minute does not sweep the sample out of a sample boat 30 disposed within the sample desorption tube 102.
  • a flow modifier 99 as shown in Figure 11 , can be threaded into the tube 96 at the end of the sample desorption tube 102 using a slot 103.
  • the flow modifier 99 has a passageway 101 extending there through so that the mercury containing gases passing through flow modifier 99 into the measurement cell 94 are induced into turbulent flow that better mixes the gas stream improving measurement precision.
  • a length of wire (not shown) can be inserted into the passageway 101.
  • several through passageways (not shown) can be provided, with one or more of the passageways angled with respect to each other.
  • the oven component 100 heats the sample being tested in sample desorption tube 102 and the resulting effluents, as discussed in more detail hereinafter, to a temperature (usually between about 590 Celsius (C) to about 680 degrees C. In this temperature range, all the elemental mercury present in the sample is converted to the gaseous phase and all the mercury compounds of interest in the sample are broken down so the mercury is in the elemental form (also gaseous) and released into the air flow through sample desorption tube 102.
  • C 590 Celsius
  • 680 degrees C In this temperature range, all the elemental mercury present in the sample is converted to the gaseous phase and all the mercury compounds of interest in the sample are broken down so the mercury is in the elemental form (also gaseous) and released into the air flow through sample desorption tube 102.
  • the elemental mercury vapor is transported, through the analytical or measurement cell 94 disposed on the optical bench 16 connected to the analyzer 12, by means of a stream of air at a constant flow rate entering the open end 102c of oven component 100 and exiting the measurement cell 94 through an outlet port 122 into line 42. This stream of air is created by the pump station 56.
  • the sample being tested is placed in a sample containment boat 30, as shown in Figures 1 , 8A and 8B .
  • the sample containment boat 30 is placed into the oven component 100 through opening 95 in a wall of the enclosed housing 92 and then into the open end 102c of the sample desorption tube 102.
  • the flow rate of air through the oven component 100 is constant.
  • the unique plumbing of the preferred embodiment allows a single pump station 56 to provide flow rates ranging from between about 0.5 L/min to about 20 L/min, and it controls the flow rates well.
  • the mercury vapor analyzer 12 can then measure the total mercury content of the sample by analyzing the beams passing through the measurement cell 94.
  • a typical sample boat 30, as shown in Figures 8A and 8B is made of a stainless steel tube 29 and with an elongated opening 31 into the tube forming an open slot 33 at the sample end 29a of the boat.
  • Stainless steel plugs 30a and 30b are provided at each end of the open slot 33.
  • a heat resistant handle 30c is disposed at the opposite end 29b of the sample boat 30 so that the sample boat can be comfortably handled even when the sample end 29a of the boat has been heated to 700 degrees C for a reasonable length of time. It is also within the terms of the preferred embodiment that traditional sample boats of quartz and ceramic can be used in the oven compartment or furnace 100.
  • the length of ideal boats 30 is such that they can be initially inserted into the furnace 100 with the sample end 29a in the first zone 102a beneath the heating coil 104 with stability and then further inserted so that the sample end 29a of the boat is disposed within the second zone 102b beneath the heating coil 106.
  • sample boats 30 made of metal can be used without shorting out the heating coils. Metal boats are more durable than those of ceramic or quartz and will not vitrify and break as quartz boats will.
  • the oven component 100 of the thermal analysis accessory 90 is illustrated with a large sample tube 102.
  • the larger design allows higher flows without disturbing the sample components placed in the sample containment boat 30; it also accommodates larger boats that can carry larger samples, and it makes all samples easier to analyze.
  • the hot sample gas is withdrawn from measurement cell 94 through outlet port 122 into line 42 by a pump station 56, as shown in Figures 1 and 10 .
  • the line 42 as shown in Figure 9 , delivers the hot sample gas to a thermo-electric cooled exhaust gas conditioner 44.
  • thermo-electric cooled, exhaust gas conditioner 44 having an inlet 130 which receives the heated exhaust gas from line 42.
  • the heated exhaust gas then flows through a line 132 connected to one end of a heat exchanger 134 and then into a line 136 which connects from the heat exchanger to an outlet 138.
  • the heat exchanger 134 quickly cools off the heated exhaust gas received from the measurement cell 94.
  • the exhaust gas conditioner 44 can be an open container 140 that contains water or some other cooling liquid. This fluid can be kept cool by a Peltier thermoelectric cooler 142 mounted outside of the container 140 with a thermal "finger" 144 which passes through the wall of the container to transfer heat from the cooling fluid to the Peltier thermoelectric cooler.
  • thermoelectric cooler 142 can be controlled by a temperature controller if necessary and can be helped by adding ice or fresh cool fluid to the cooling fluid within the container 140.
  • the exhaust gas conditioner 44 can also be used without the thermoelectric cooler 142 if desired and appropriate.
  • the heat exchanger 134 is oriented such that the flow of exhaust gas is not impeded by condensate.
  • the thermo-electric cooled, exhaust gas conditioner 44 has a gas-to-water heat exchanger 134 that is immersed in water or other cooling fluid that is kept cool by a Peltier thermoelectric cooler 142.
  • the heat exchanger 134 can incorporate a drain valve (not shown) to occasionally purge the heat exchanger of condensate. However, it is noted that the drain valve is not needed for the operation of the preferred embodiment.
  • the exhaust gas conditioner 44 is preferably located close to the furnace exhaust through outlet port 122 so that the excess moisture in the sample gas condenses quickly thus minimizing any flow variations at the time when the mercury is being released from the sample.
  • the exhaust gas conditioner 44 also cools the sample exhaust gases to a relatively consistent temperature that helps improve precision in flow and hence analyzer precision. Moisture in samples and especially aqueous standards for analysis can cause variations in flow and hence response as water expands and contracts as it changes state from water to steam and back again to water. The exhaust gas conditioner 44 minimizes the effect of this variation in flow.
  • the flow of exhaust gas from the outlet port 138 of exhaust gas conditioner 44 flows through a line 46 into a filter 48 which contains soda lime, iodinated charcoal and or charcoal to scrub the exhaust gases of acid gases and mercury.
  • the exhaust gas continues through line 50 into a mass flow controller 52 such as an Alicat Whisper series laminar flow element mass flow controller, that can precisely control the flow despite the system's inherent low differential pressure.
  • the mass flow controller 52 has the ability to regulate flow by mass or volume.
  • the exhaust gas continues from the mass flow controller 52 and into a vacuum pump station 56 through a line 54.
  • the pump station 56 induces the flow of gas through the furnace 100 and the measurement cell 94.
  • the exhaust gas exits the pump within the pump station 56 though a muffler which suppresses the noise of the exhaust.
  • the pump station 56 includes a high powered pump which can pump >20 liters/minute while the present embodiment may often only require a flow rate of a fraction of this amount. Therefore, the pump station 56 includes an air inlet (not shown) that can be controlled to allow more or less air into the pump to mix with the gases from line 54 to prevent the pump from "throttling" at such low flows.
  • the thermal desorption furnace 100 as shown in Figure 6 , has many features that make it unique and make the analysis of samples (especially sorbent traps for mercury) easier and with improved precision and accuracy.
  • the sample desorption tube can be made of durable metal which should never break or leak like a sample tube of quartz or ceramic.
  • furnace 100 helps with the analysis of high concentration samples.
  • an exhaust gas conditioner 44 for the sample gases exiting from the outlet 122 of the thermal analysis cell 94 quickly forces the condensation of water vapor in the sample effluent and allows more uniform control of the gas temperature going to the laminar flow element mass flow controller and vacuum pump to thereby provide more precise flow and hence better analytical results.
  • thermoelectric cooler 142 can be controlled by a temperature controller if necessary and can be helped by adding ice or fresh cool fluid to the cooling fluid within the container 140.
  • the exhaust gas conditioner 44 can also be used without the thermoelectric cooler 142 if desired and appropriate.
  • the furnace (100) is used when measuring the amount of mercury present in a sample placed into the sample boat (30), including higher level aqueous samples, complex samples such as oils, solid samples including sorbent traps used to measure the mercury content of emission sources, and gas streams introduced into the furnace directly.
  • the desired amount of sample is measured by mass or volume and placed directly into the sample boat or onto a bed of mercury-free charcoal that is first placed in the boat. The sample is then covered with a layer of sodium carbonate and placed in the furnace for analysis.
  • the furnace 100 is particularly useful when analyzing sorbent traps, such as a speciation trap 145.
  • a sorbent trap such as the speciation trap 145 can be a glass tube with different sections of media separated by glass wool 151.
  • section 146 can be filled with an acid gas scrubber
  • sections 147 and 148 can be filled with potassium chloride
  • sections 149 and 150 can be filled with iodinated carbon.
  • Each section 146, 147, 148, 149 and 150 can be enclosed on either side with glass wool 151. In operation, the contents of the trap are removed and each individual section along with the glass wool that precedes it is placed in a sample boat 30 and covered with sodium carbonate and analyzed.
  • the potassium chloride sections are wrapped in aluminum foil along with the glass wool that precedes them before being placed in the sample boats 30 and then covered with sodium carbonate. This prevents the sodium carbonate and potassium chloride from mixing and allows the samples to be analyzed more quickly at higher temperatures. Transferring the contents of the sorbent traps to the sample boats can be tedious and the use of larger sample boats in this design makes this process easier.
  • a sample boat 30 with the media from one section and covered with sodium carbonate is then inserted into the opening 102c of the sample desorption tube 102.
  • a flow of about 0.5 L/min to about 20 L/min can be used in this design allowing a variability of sensitivity at a factor of >40.
  • Typical samples might be analyzed with both zones 102a and 102b heated by coils 104 and 106, respectively, for example at 680 degrees C.
  • the sample boat 30 can be first placed in the first heated zone 102a heated by coil 104 that could be set at a low temperature, such as 480 degrees C. Once enough mercury has been released, as indicated on the computer 14 so that the analyst is confident that the detector 12 will not be over-saturated, the boat is moved further into the higher temperature heated zone 102b heated by coil 106, such as at 680 degrees C. In this way, these high-level samples can be analyzed in a fraction of the time as compared to previous designs that used a ramping feature on the furnace to lower and raise the furnace temperature.
  • sample desorption tube 102 with two heated zones 102a and 102b heated by different heat coils 104 and 106 capable of two separate temperatures is advantageous when analyzing samples of various types, some requiring analysis at low temperatures and some requiring analysis at high temperatures because samples requiring analysis at lower temperatures can be analyzed solely in the first heated zone, such as at about 590 degrees C. While with other samples best analyzed at higher temperatures, they can be analyzed using the hotter second heated zone using the same calibration and without having to wait for a single heated zone to cool down and heat up. With these two zones set at constant temperatures throughout an analytical session, the analyzer system 10 is more precise than one that ramps the temperatures from cooler to hotter because such ramping affects the flow of the sample gases.
  • high-level samples can be analyzed at flow rates of 20 L/min or more, they can be done isothermally in minimal time, as little as 90 seconds, compared to using a low flow rate of approximately 4 L/min which requires having to ramp the furnace to slow the mercury elution which can take as long as 15-20 minutes per sample.
  • the external isolated heater coils 104 and 106 are virtually maintenance-free and don't become choked with debris as with the prior art internal "live" coils.
  • thermocouples, relays, and PID temperature controllers means that a failure of any component can be overcome in use by best configuring the remaining pieces to allow the instrument's continued use. This is a significant reliability advantage especially if the instrument is used in the field where repairs might be more difficult.
  • FIG. 13 there is illustrated a schematic of an aqueous sample device 180 disclosed herein that uses a larger reaction vessel or impinger 182 to get better detection limits.
  • the aqueous sample device 180 as shown in Figure 13 , consists of a measurement cell 184 which includes a tube 185 made of a material that resists the adsorption of mercury.
  • the length of tube 185 when used with a suitably configured long optical bench, would be about 30 cm long. Alternatively, if the tube 185 is used with the standard optical bench shown, its length would be about 10 cm long.
  • the tube 185 is sealed on both ends with lenses 186 and 188 made of quartz or another material transparent to the wavelengths of the beam(s) used, with an outlet 190 on one side that is connected through line 191 to a vacuum pumping system 195 (compare pump system 56 shown in Figure 10 ) and an inlet 192 on the other side connected by a line 193 to an impinger 182 where aqueous samples are introduced and mixed with a stannous chloride solution by the turbulence of the incoming air.
  • the impinger 182 includes a vessel 194 closed with a cap 196 having an air inlet 197 and an outlet 198.
  • a tube 199 extends from the air inlet to the stannous chloride solution 200 disposed in the bottom of vessel 194.
  • An optical bench similar to optical bench 16 is mounted to a mercury vapor analyzer, such as described previously, in a path traveled by the analytical beams projected out of the vapor analyzer whereby the analytical beams traverse the measurement cell, interact with the sample effluent of the impinger directed into the cell from the outlet of the impinger and out of the cell through the outlet of the cell.
  • the aqueous sample device 180 is unique in that the measurement cell 184 is made to easily fit in either a larger configured optical bench or the standard optical bench, as shown in Figure 2 , which can also be used for the analysis of samples of other matrices. In either case, detection limits are much lower than achieved by using the standard cell, approximately 6 cm in length, because the measurement cell for this instrument uses the dual path optical bench instead of the single path optics used for the standard 6 cm cell.
  • a standard stannous chloride reduction system is used for aqueous samples.
  • the length of the larger configured optical bench is designed to be long enough to allow low concentration ( ⁇ 1 ng/L) water sample analysis in a robust measurement cell 180.
  • the analyzer 12 can be used for this analysis by using its internal multi-pass cell. But, whereas if liquid water is accidentally allowed to enter the cell, many thousands of dollars of damage can take place, and therefore, the measurement cell is designed so that it can simply be cleaned and dried.
  • the present disclosure can also be made to work in the detection of any metal that entirely converts to the gaseous phase and elemental form at the temperatures the oven is capable of generating.
  • any metal that entirely converts to the gaseous phase and elemental form at the temperatures the oven is capable of generating Whereas mercury is very unique because it is a liquid at ambient temperature, other metals such for example, selenium might also be measured in this way.
  • the main advantage of the present attachment disclosure is the ease with which the limits can be reached. That is to say, detection limits are not much improved, but, in it's final form, the present disclosure will be able to quantify samples at a level of 1/2 to 1/4 of any present commercial mercury analysis unit, which isn't a significant improvement given that quantification limits are already on the order of 100 or 200 picograms of mercury.
  • one advantage of the present attachment is that the sample boats 30 can be much larger than those that are presently used, which perforce means that the detection limits in the terms of concentration will be lower with the present embodiment because more sample material can be placed in the boat.
  • the sample boat can have an elongated opening 30 as seen in figs.
  • the preferred embodiment can quantify 100,000 ng (i.e., 100 ug). It could even be configured to handle larger samples and higher detection limits, were that deemed to be worthwhile. That is to say, while the current commercial units can analyze 100,000 ng, each analytical run takes on the order of 15 minutes. By contrast, the preferred embodiment is designed to do the same analysis in 3 to 4 minutes. In use, if 30 or more samples plus about 6 standards are to be analyzed, there is a huge efficiency improvement in analysis turn-around time.
  • the thermal method of mercury analysis is enormously better than other techniques especially when combined with an atomic absorption spectrometer employing Zeeman correction.
  • Samples can be analyzed in seconds or minutes with no or little sample preparation.
  • Lumex and Ohio Lumex pretty much monopolize the present market, and lots of mercury work is being done around the world.
  • the preferred embodiment is much more efficient in terms of time saved and ease of maintenance; it can analyze samples in a fraction of the time with less work, and is more precise as well.
  • Typical analyzers for this type of analysis have very small sample boats that limit sample volume and make it time consuming and difficult to place the sample in the boat.
  • the sample desorption tube 102 is so large, at least 1.5 inches in diameter, is made of metal, and incorporates heater coils that are electrically insulated and wound about the outside of the sample desorption tube, the sample boats can be made of stainless steel or other durable metal and can be large enough that sample preparations take less than half the time or better.
  • the analyzer system 10 uses a unique combination of a laminar flow element-mass flow controller 52 and a specially designed pump station 56 to allow precise instrument flow at all flow rates. Also incorporated in the flow path is a muffler to quiet the pump exhaust and a filter to scrub the instrument's exhaust of mercury and acid gases.
  • Flow is initially induced through the system 10 by the use of a Rolling Diaphragm vacuum pump (not shown) disposed within the pump station 56.
  • the Rolling Diaphragm vacuum pump is fitted with a dual ball bearing motor shaft to add reliability and long life.
  • the exhaust from the vacuum pump is directed into an "L"-shaped muffler (not shown) to dampen the pump's noise.
  • the vacuum pump is also mounted to the pump box in an isolated fashion and surrounded by sound insulating materials and suitably positioned sound baffles to limit noise. A fan in the pump box keeps the vacuum pump cool and helps direct exhaust out of the enclosure.
  • the vacuum pump's inlet is connected to a fitting splitting the inlet flow between two paths; one is to a valve and meter open to atmosphere that can be adjusted from a flow of zero to maximum flow.
  • the other is connected to the laminar flow element mass flow controller 52, which can precisely control the flow according to mass or volume as chosen on its keypad.
  • a suitable instrument flow is selected on the control pad of the laminar flow element mass flow controller 52 and if this rate is small compared to the maximum flow of the pump (for example, less than 10 L/min), the valve on the other meter is open to allow the vacuum pump to pull air through this path as well to avoid having the pump "throttled" by operating at too low a flow rate.
  • the laminar flow element mass flow controller can regulate the flow through the instrument from ⁇ 1.0 L/min to over 20 L/min.
  • the other valve is adjusted to prevent the pump "throttling” but to be restrictive enough so that the laminar flow element mass flow controller 52 can achieve its desired setting.
  • the inlet of the laminar flow element mass flow controller 52 is connected to a filter element 48 that contains iodinated charcoal and, or charcoal to scrub the instrument's exhaust of mercury and other effluents and soda lime to assure that no acid gases reach the laminar flow element mass flow controller 52 or pump.
  • This instrument can also be used for discrete or continuous measurement of mercury (or other suitable analytes) in gas streams such as emission sources by directing either a diluted or undiluted flow of the gas stream in question into the sample desorption tube making sure that the volume of gas introduced is less than the volume of gas exiting the furnace to assure none of the sample is lost by exiting the entrance.

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Claims (13)

  1. Système d'analyseur (10) pour mesurer le mercure comprenant :
    un analyseur de vapeur de mercure (12) pour générer et détecter des faisceaux analytiques ;
    un banc optique (16) monté sur un analyseur de vapeur de mercure (12) dans lequel une cellule de mesure (22, 184) peut être positionnée de sorte que les faisceaux analytiques peuvent traverser la cellule de mesure, interagir avec un gaz effluent d'échantillon et revenir vers l'analyseur de vapeur où la quantité de mercure dans le gaz effluent d'échantillon peut être déterminée ;
    une station de pompe (56) pour retirer le gaz effluent d'échantillon de la cellule de mesure ;
    un four (24) monté sur la cellule de mesure (22) ; et
    une capsule de prélèvement (30) destinée à contenir un échantillon, adaptée pour être disposée à l'intérieur du four pour libérer le gaz effluent d'échantillon de l'échantillon dans la cellule de mesure ;
    caractérisé par :
    un modificateur de gaz d'échappement (44) pour recevoir le gaz effluent d'échantillon de la cellule de mesure et pour refroidir le gaz d'échantillon afin de condenser toute humidité en excès transportée dans le gaz d'échantillon, dans lequel le modificateur de gaz d'échappement (44) comprend :
    un échangeur de chaleur (134) qui reçoit et refroidit un gaz d'échappement chaud de la cellule de mesure (22) ; et
    un refroidisseur thermoélectrique (142) pour refroidir le fluide à l'intérieur du modificateur de gaz d'échappement (44) de sorte que le refroidissement du gaz d'échantillon retiré de la cellule de mesure à l'environnement proche améliore la régulation du gaz retiré de la cellule de mesure.
  2. Système d'analyseur (10) selon la revendication 1, dans lequel le banc optique (16) comprend :
    un tube creux (78) monté au niveau d'une première extrémité du banc optique (16) à travers lequel les faisceaux analytiques en saillie de l'analyseur de vapeur sont dirigés à travers la cellule de mesure qui est positionnée dans ledit banc optique monté sur l'analyseur de vapeur (12) ;
    un prisme (82) monté au niveau d'une seconde extrémité du banc optique (16) pour ramener les faisceaux analytiques qui traversent la cellule de mesure jusqu'à l'analyseur (12) ;
    dans lequel le banc optique est adapté pour être utilisé avec un dispositif d'échantillonnage thermique et aqueux ; et
    une lentille (84) pour concentrer les faisceaux analytiques revenant du prisme (82) à travers le tube creux (78) jusqu'à un détecteur optique (20) dans l'analyseur (12).
  3. Système d'analyseur (10) selon la revendication 1, dans lequel le four (24) comprend :
    un tube de désorption d'échantillon allongé (102) raccordé au niveau d'une extrémité, par un raccord tubulaire (96), à la cellule de mesure (22), le tube de désorption d'échantillon ayant une ouverture (102c) au niveau d'une extrémité opposée pour recevoir la capsule de prélèvement (30) ; et
    le tube de désorption d'échantillon (102) étant assez grand de sorte qu'un débit élevé compris entre environ 4 l/minute et 40 l/minute ne balaie pas l'échantillon de la capsule de prélèvement (30) disposée à l'intérieur du tube de désorption d'échantillon.
  4. Système d'analyseur (10) selon la revendication 3, comprenant en outre un modificateur d'écoulement (99) dans le raccord tubulaire (96) afin d'induire l'écoulement turbulent dans le gaz effluent d'échantillon passant du tube de désorption d'échantillon (102) à la cellule de mesure (22).
  5. Système d'analyseur (10) selon la revendication 3, dans lequel :
    une première bobine de chauffage par résistance (104) pliable est enroulée autour de l'extérieur d'une première section (102a) du tube de désorption d'échantillon (102) ; et
    une seconde bobine de chauffage par résistance (106) pliable est enroulée autour de l'extérieur d'une seconde section (102b) du tube de désorption d'échantillon (102) ; et
    dans lequel les première et seconde bobines de chauffage par résistance (104, 106) sont raccordées à un organe de commande de four (32) pour contrôler la température dans chacune des première et seconde sections (102a, 102b).
  6. Système d'analyseur (10) selon la revendication 1, comprenant le four (24) et la capsule de prélèvement (30), dans lequel :
    la capsule de prélèvement (30) est un tube (29) fermé à chaque extrémité et ayant une ouverture allongée (31) entre eux formant une fente ouverte (33) entre les extrémités fermées du tube pour recevoir l'échantillon à analyser ;
    la capsule de prélèvement (30) est construite à partir d'acier inoxydable ; et
    la capsule de prélèvement a une longueur comprise entre 19 cm et environ 24 cm et un diamètre compris entre 16 mm et environ 20 mm.
  7. Système d'analyseur (10) selon l'une quelconque des revendications précédentes, dans lequel la cellule de mesure (22, 184) est scellée sur deux extrémités par des joints et des fenêtres transparentes aux longueurs d'onde des faisceaux analytiques utilisés, maintenus en place avec des capsules à vis.
  8. Système d'analyseur (10) selon la revendication 1, comprenant en outre un filtre (48) pour recevoir les gaz d'échantillon refroidis du modificateur de gaz d'échappement (44) et pour nettoyer les gaz d'échantillon de gaz acides et de mercure.
  9. Système d'analyseur (10) selon la revendication 8, comprenant en outre un régulateur de débit massique d'élément d'écoulement laminaire (52) qui reçoit les gaz d'échantillon refroidis du filtre (48) et régule l'écoulement de gaz par le biais du système d'analyseur malgré la faible pression différentielle entre une entrée et une sortie du régulateur de débit massique.
  10. Système d'analyseur (10) selon la revendication 1, dans lequel :
    la station de pompe (56) induit l'écoulement du gaz d'échantillon à travers le four (24) et la cellule de mesure (22) ;
    la station de pompe est raccordée de sorte qu'elle peut fonctionner à des débits d'au moins 1,0 l/min à 20 I/min, et
    la pompe est une pompe à membrane à roulement avec un arbre de moteur à double roulement à billes.
  11. Procédé pour mesurer la vapeur de mercure comprenant les étapes suivantes :
    générer des faisceaux analytiques avec un analyseur de vapeur de mercure (12) ;
    libérer le gaz effluent d'échantillon d'un échantillon dans une cellule de mesure (22, 184) ;
    faire faire saillie aux faisceaux analytiques par rapport à l'analyseur de vapeur en passant par la cellule de mesure afin d'interagir avec le gaz effluent d'échantillon et ramener les faisceaux analytiques à l'analyseur de vapeur où la quantité de mercure dans le gaz effluent d'échantillon peut être déterminée ; et
    retirer le gaz effluent d'échantillon de la cellule de mesure,
    dans lequel le gaz effluent d'échantillon est généré en chauffant l'échantillon dans une capsule de prélèvement (30) disposée à l'intérieur d'un four (24) ;
    caractérisé par les étapes suivantes :
    recevoir et faire refroidir le gaz effluent d'échantillon reçu de la cellule de mesure dans un modificateur de gaz d'échappement (44) afin de condenser toute humidité en excès transportée dans le gaz d'échantillon, dans lequel :
    un échangeur de chaleur (134) du modificateur de gaz d'échappement (44) reçoit et refroidit un gaz d'échappement chaud de la cellule de mesure (22) ; et
    un refroidisseur thermoélectrique (142) du modificateur de gaz d'échappement (44) refroidit le fluide à l'intérieur du modificateur de gaz d'échappement (44) de sorte que le refroidissement du gaz d'échantillon retiré de la cellule de mesure à l'environnement proche améliore la régulation du gaz retiré de la cellule de mesure.
  12. Procédé selon la revendication 11, dans lequel le gaz effluent d'échantillon est généré en chauffant l'échantillon dans la capsule de prélèvement (30) à l'intérieur du four (24), comprenant en outre les étapes suivantes :
    chauffer la capsule de prélèvement (30) à l'intérieur du four (24) ayant une première section de chauffage (26) et une seconde section de chauffage (28) ; et
    contrôler séparément la température dans chacune des première et seconde sections de chauffage.
  13. Procédé selon la revendication 12, dans lequel l'étape pour analyser un échantillon chauffé dans une capsule de prélèvement (30) comprend les étapes suivantes :
    enrouler les sections de chlorure de potassium d'un piège de spéciation dans une feuille ;
    placer la feuille enveloppant les sections de chlorure de potassium dans une capsule ; et
    recouvrir avec du carbonate de sodium.
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10029290B2 (en) 2013-11-04 2018-07-24 Loci Controls, Inc. Devices and techniques relating to landfill gas extraction
US10576514B2 (en) 2013-11-04 2020-03-03 Loci Controls, Inc. Devices and techniques relating to landfill gas extraction
WO2015108820A1 (fr) * 2014-01-14 2015-07-23 The Regents Of The University Of California Procédé et dispositif de détection et de cartographie spatiale d'une concentration de mercure dans des échantillons d'eau
CN105092866B (zh) * 2015-08-20 2017-05-10 长沙开元仪器股份有限公司 一种自动测汞装置
US10705063B2 (en) 2016-03-01 2020-07-07 Loci Controls, Inc. Designs for enhanced reliability and calibration of landfill gas measurement and control devices
CA3240725A1 (fr) 2016-03-01 2017-09-08 Loci Controls, Inc. Conceptions pour une fiabilite et etalonnage ameliores de dispositifs de mesure et de commande de gaz d'enfouissement
CN105606555A (zh) * 2016-03-10 2016-05-25 山东五洲检测有限公司 一种水中汞离子含量的检测方法
US10946420B2 (en) 2018-03-06 2021-03-16 Loci Controls, Inc. Landfill gas extraction control system
WO2020072457A1 (fr) 2018-10-01 2020-04-09 Loci Controls, Inc. Systèmes et procédés d'extraction de gaz de décharge
CN110261311A (zh) * 2019-07-29 2019-09-20 南京诺尔曼生物技术有限公司 激发物保温装置
CN111220789A (zh) * 2020-01-21 2020-06-02 山东大学 Tbm搭载的利用汞进行超前地质预报的系统及方法
US11883864B2 (en) 2020-01-29 2024-01-30 Loci Controls, Inc. Automated compliance measurement and control for landfill gas extraction systems
US11623256B2 (en) 2020-07-13 2023-04-11 Loci Controls, Inc. Devices and techniques relating to landfill gas extraction
US12090532B2 (en) * 2020-07-13 2024-09-17 Loci Controls, Inc. Devices and techniques relating to landfill gas extraction
CA3202802A1 (fr) 2020-12-03 2022-06-09 Loci Controls, Inc. Controle d'emissions de gaz a effet de serre

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS581149U (ja) * 1981-06-26 1983-01-06 日本インスツルメンツ株式会社 排煙の水銀検出装置

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3281596A (en) * 1964-03-23 1966-10-25 Cordero Mining Company Method of detecting mercury vapor by collecting the mercury and thereafter analyzing the collected mercury by ultraviolet absorption analysis
DE3919042A1 (de) 1989-06-10 1990-12-13 Bodenseewerk Perkin Elmer Co Verfahren und vorrichtung zur analyse von festen substanzen auf quecksilber
US5619041A (en) 1994-06-01 1997-04-08 Bodenseewerk Perkin-Elmer Gmbh Atomic absorption spectrometer for measuring the mercury concentration in a sample
DE19506875C1 (de) 1995-02-17 1996-10-31 Harbauer Gmbh & Co Kg Verfahren und Vorrichtung zur schnellen Bestimmung der Quecksilberkonzentration in Feststoffen
US5879948A (en) 1997-05-12 1999-03-09 Tennessee Valley Authority Determination of total mercury in exhaust gases
US6223584B1 (en) * 1999-05-27 2001-05-01 Rvm Scientific, Inc. System and method for vapor constituents analysis
US6736883B2 (en) 2001-12-14 2004-05-18 Apogee Scientific, Inc. Particulate separation system for mercury analysis
CA2480531C (fr) * 2003-09-22 2012-06-12 Tekran Inc. Systeme et methode de conditionnement pour la mesure du mercure dans des emissions gazeuses
US7454952B2 (en) 2005-05-02 2008-11-25 Thermo Fisher Scientific Inc. Method and apparatus for monitoring mercury in a gas sample
RU2373522C1 (ru) 2008-05-26 2009-11-20 Общество с ограниченной ответственностью "ВИНТЕЛ" Атомно-абсорбционный ртутный анализатор
JP2010096688A (ja) 2008-10-20 2010-04-30 Nippon Instrument Kk 水銀分析のための加熱分解装置および水銀分析装置ならびにその方法
DE202010002443U1 (de) 2010-02-17 2010-05-06 Mikrowellen-Systeme Mws Gmbh Vorrichtung zur Bestimmung eines Quecksilbergehalts einer Probe
US9075634B2 (en) 2010-07-12 2015-07-07 International Business Machines Corporation Minimizing overhead in resolving operating system symbols
EP2482057B1 (fr) 2011-01-27 2013-03-20 Sick Ag Analyseur de gaz destiné à la mesure de la teneur en mercure d'un gaz et procédé de calibration

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS581149U (ja) * 1981-06-26 1983-01-06 日本インスツルメンツ株式会社 排煙の水銀検出装置

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US20160123946A1 (en) 2016-05-05

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